Oil and fuel compositions containing epoxidized terpolymer derivatives

ABSTRACT

1. A COMPOSITION COMPRISING A MAJOR AMOUNT OF A HYDROCARBON FUEL OR LUBRICATING OIL AND .001 TO 45 WT. PERCENT OF AN OIL SOLUBLE ADDUCT OF AN EPOXIDIZED TERPOLYMER, USEFUL AS A LUBRICANT OR FLUEL ADDITIVE, SAID TERPOLYMER HAVING A MOLECULAR WEIGHT IN THE RANGE OF 10.000 TO 1,000,000 VISCOSITY AVERAGE MOLECULAR WEIGHT AND COMPRISING IN THE RANGE OF ABOUT 30 TO 85 MOLE PERCENT ETHYLENE, ABOUT 14.5 TO ABOUT 69.5 MOLE PERCENT OF A C3 TO C8 ALPHA MONOOLEFIN AND ABOUT 0.5 TO ABOUT 20 MOLE PERCENT OF A C5 TO C14 NON-CONJUGATED DIOLEFIN, WHEREIN ABOUT 10 TO 100% OF THE DOUBLE BONDS IN THE TERPOLYMER HAVE BEEN EPOXIDIZED, AND ABOUT 10 TO 100% OF THE EPOXIDIZED GROUPS HAVE BEEN REACTED WITH A C1 TO C18 AMINE WHICH CONTAINS 1 TO 8 NITROGEN ATOMS TO FORM SAID ADDUCT.

United States Patent O 3,842,010 OIL AND FUEL COMPOSITIONS CONTAININGEPOXIDIZED TERPOLYMER DERIVATIVES James J. Pappas, Parsippany, NormanJacobsen, East Brunswick, and Edward N. Kresge, Watchung, N.J.,assignors to Esso Research and Engineering Company, Linden, NJ.

No Drawing. Continuation-impart of abandoned application Sacr. No.235,439, Mar. 16, 1972. This application Mar. 2, 1973, Ser. No. 337,460

Int. Cl. Cm 1/32, 1/38 US. Cl. 252-515 R 6 Claims ABSTRACT OF THEDISCLOSURE Terpolymers of ethylene, a C to C alpha-olefin and anon-conjugated acyclic or alicyclic diolefin are epoxidized at sites ofunsaturation which are extraneous to the main backbone chain of carbonatoms. Either the epoxidized terpolymer or the reaction products of theepoxidized terpolymer With reagents having replaceable hydrogen, i.e.,water, organic acids, alcohols, amines, phenols, mercaptans and thelike, are useful as multifunctional additives for synthetic and mineraloil lubricants and fuels.

RELATED APPLICATION This application is a continuation-in-part of ourprior application Ser. No. 235,439, filed Mar. 16, 1972, now abandoned.

BACKGROUND OF THE INVENTION Field of the Invention The present inventionrelates to epoxidized terpolymers and functional derivatives obtainedtherefrom and their use in lubricant compositions, for example, assludge dispersants and viscosity index improvers. More particularly, theinvention is directed to epoxidized terpolymers of ethylene, C -Cu-olefins and non-conjugated dienes in which the chain of carbon atomsforming the terpolymer backbone is essentially saturated and anysubstantial unsaturation in the terpolymer, prior to epoxidation, is inan alkylene radical pendant to the backbone or is pendant to or part ofa cyclic structure attached to the backbone. The epoxidized terpolymermay be further reacted with a functional reagent which is herein definedas a reagent having a replaceable hydrogen which will react with anoxirane in the presence of an acidic or basic catalyst to form afunctional adduct. The oil-soluble epoxidized terpolymers or itsfunctional adducts are useful as additives for lubricants, such assludge dispersants and viscosity index improvers, and as sludgedispersants in mineral oil fuels, e.g., distillate fuel oil andgasoline.

Description of the Prior Art Epoxidation of polymers of butadiene andcopolymers of butadiene and styrene, in each instance of which apreponderant proportion of the unsaturation in the polymers is locatedin the chain backbone, has been described in US. Pat. 2,829,135 and inBritish Pat. No. 774,752 and 774,765. The resinous products obtainedwere useful in the formulation of surface coatings.

US. Pat. 3,388,067 is of interest in demonstrating the improvements ofthe present invention over the prior art. This patent describes theoxidation, preferably in the presence of a free-radical initiator, of anessentially saturated copolymer of ethylene and propylene at tertiaryhydrogen sites located on the polymer backbone chain.

ice

Cleavage of the polymer chain occurs with the formation ofhydroperoxidized segments of lower molecular weight polymer. Subsequentreduction of the hydroperoxidized segments yields a polymer hydroxylatedon the backbone chain, useful as a viscosity index improver.

SUMMARY OF THE INVENTION In contrast to the products of the prior art ithas now been discovered that terpolymers of ethylene, one or more alphamonoolefins having from 3 to 8 carbon atoms, preferably propylene, and astraight or branched chain acyclic, or alicyclic non-conjugateddiolefin, in which the unsaturation in the terpolymer, originating fromthe diolefin incorporated therein is extraneous to the main polymerchain and is either pendant to or part of a cyclic structure attached toan essentially saturated backbone chain, when epoxidized, or epoxidizedand further reacted with a functional reagent having a replaceablehydrogen to form a functional adduct, yields products having the samechain length as the original terpolymer, which are useful as sludgedispersants, viscosity index improvers and acidity neutralizers whenincorporated into lubricants.

Terpolymers, useful for formation of the epoxidized products of thisinvention contain at least 30 mol. percent, preferably not more than 85mol. percent of ethylene; between about 15 e.g., 14.5 and about 70, e.g.69.5 mol. percent of a higher alphaolefin or mixture thereof, preferablypropylene; and between 0.5 to 20 mol. percent, preferably 1 to 15 mol.percent, of a non-conjugated diolefin or mixture thereof. Especiallypreferred are polymers of about 40 to mole percent ethylene, 20 to 58mole percent higher monoolefin and 2 to 10 mole percent diolefin. On aweight basis, usually the diolefin will be at least 2 or 3 wt. percentof the total terpolymer. Structures of a number of useful terpolymersare illustrated below.

DESCRIPTION OF THE PREFERRED EMBODIMENTS l Terpolymers Ethylenepropylene-non-conjugated diolefin terpolymers are well known articles ofcommerce. The preparation of typical terpolymers, using Ziegler-Nattacatalysts, is described for example in US. Pats. 2,933,480; 3,000,- 866;and 3,093,621. These terpolymers, which are pri marily produced for usein elastomeric compositions, are characterized by the absence of chainor backbone unsaturation and contain sites of unsaturation in groupswhich are pendant to or are in cyclic structures outside of the mainpolymer chain. These structures render the polymers particularlyresistant to breakdown by atmospheric oxidation or ozone.

Useful terpolymers for the production of the epoxidized products of thisinvention comprise ethylene, a C to C straight or branched chainalpha-olefin and a nonconjugated diolefin. Representative non-limitingexamples of non-conjugated diolefins that may be used as the thirdmonomer in the terpolymer include:

(A) Straight chain acyclic dienes such as: 1,4-hexadiene;1,5-heptadiene, 1,6-octadiene.

(B) Branched chain acyclic dienes such as: S-methyl- 1, 4-hexadiene;3,7-dimethyl 1,6-octadiene; 3,7-dimethyl 1,7-octadiene; and the mixedisomers of dihydro-myrcene and dihydroocimene.

(C) Single ring alicyclic dienes such as: 1,4-cyclohexadiene;1,5-cyclo-octadiene; 1,5-cyclododecadiene, 4- vinyl-cyclohexene; l-allyl4-isopropylidene cyclohexane; 3-allyl-cyclopentene; 4-allyl cyclohexeneand l-isopropenyl 4-(4-butenyl) cyclohexane.

D) Multi single ring alicyclic dienes such as: 4,4- dicyclopentenyl and4,4-dicyclohexenyl dienes.

(E) Multi-ring alicyclic fused and bridged ring dienes such as:tetrahydroindene; methyl tetrahydroindene; dicyclopentadiene;bicyclo(2,2,1) hepta 2,5-diene; alkenyl, alkylidene, cycloalkenyl andcycloalkylidene norbornenes such as: S-methylene 2 norbornene; 5ethylidene 2- norbornene; S-methylene-6-methyl-2-norbornene;5-methylene-6,6-dimethyl-2-norbornene; 5-propenyl-2 norbornene;5-(3-cyclopentenyl)-2-norbonene and 5-cyclohexyldene-Z-norbornene.

In general useful terpolymers contain non-conjugated diolefins having 5to 14 carbon atoms and exhibit viscosity average molecular weights (fiof from 10,000 to 1,000,000, e.g., 20,000 to 200,000, as determined inDecalin solvent at 135 C. In addition, the molecular weightdistributions of the useful terpolymers are preferably narrow, havingweight average to number average molecular Weight ratios of less than 15and preferably less than 10.

Structurally, the terpolymers suitable for conversion to the epoxidesand their functional adducts of the present invention may be illustratedfor various non-conjugated diene monomers as random terpolymers in whichthe following moieties are linked in the polymer chain in a randomsequence and in a varying number.

m r r WWQHPQHQWCHFCHWCHFCHW x A H2CCH=CHCH3 Higher Ethylene a-olefin1,4-hexadiene units units units \A I A HCCH2CH HCCH /CH HC=OH EthyleneDicyclopentadiene Higher-aunits units olefin units oo cn,on -oHi-cni A lA A HCCH;OH

H2CC=CH-CH3 5-ethylidene-2-nor- Higher-ot- Ethylene bornene olefin unitsunits in which x, y and z are cardinal numbers, typically in the rangeof 1 to 100. While these terpolymers are essentially amorphous incharacter by superficial inspection, they may contain up to about 25percent by weight of crystalline segments as determined by X-ray ordifferential scanning calorimetry. Details of these methods formeasurement of crystallinity are found in J. Polymer Sci., A-2, 9, T27(1971) by G. Ver Strate and Z. W. Wilchinsky. On epoxidation, an oxiraneis formed at either all or part of the unsaturation, shown above as adouble bond.

(2) Ep oxidation While commercially available terpolymers, asillustrated structurally above having the requisite level ofuns-aturation and molecular weight may be used to prepare the epoxidizedterpolymers of this invention, by dissolving the polymer in a suitablesolvent before proceeding with the epoxidation, convenience andeconomies in operation may be effected by epoxidizing the terpolymerwhile it is in cement form, as it is normally recovered from the polymersynthesis. Since the media used for dissolving or dispersing thecatalyst components and terpolymer reaction products in theZiegler-Natta synthesis are also suitable for the epoxidation reaction,the use of a deactivated, polymer cement freed of catalyst residues,recovered from the synthesis reaction is especially attractive.

Suitable solvents may be selected from the general group of olefin-freepetroleum hydrocarbons, aromatics and halogenated hydrocarbons. C orlower, straight or branched chain saturated hydrocarbons are preferred,but C to C saturated alicyclic, or C to C aromatic hydrocarbons may beused with equal facility. Halogenated hydrocarbons having two to sixcarbon atoms in the molecule are also useful. Representativenon-limiting examples include: pentane, cyclopentane, normal andisohexane, heptane, isooctane, methyl cyclopentane, benzene, toluene,mixed xylene, dichloroethane, trichloroethane, orthodichlorobenzene, andmixtures of the above.

Depending on the viscosity of the resulting solution and the reagentused to effect epoxidation, a concentration in the range of 1 to 10percent by weight of terpolymer in solvent may conveniently be used forconversion of the terpolymer to epoxide.

A Wide variety of reagents and techniques may be used for elfecting theepoxidation of the preferred terpolymers. As an illustration of this, apartial list of reagents and techniques is described in OrganicReact-ions, vol. 7, p. 378 by Daniel Swern, John Wiley and Sons, NewYork, 1953. The particular reagent or method used is one of economicsand convenience and is not a limiting aspect of this invention and manyvariations from the examples shown below will be apparent to thosehaving skill in the art. Typical reagent-s include: perbenzoic acid,metachloroperbenzoic acid, peracetic acid, trifiuoroperacetic acid,monoperphthal-ic acid, performic ac-id, hydrogen peroxide-acetic acid,and hydrogen peroxide-formic acid.

Usually, from 10 to preferably 40 to 98% of the double bonds in theterpolymer will be converted to oxirane groups. Since it is uneconomicalfor practical purposes to attempt to convert all of the double bonds inthe terpolymer molecule to an oxirane, the structure of one particularembodiment of an epoxidized terpolymer may in which x is a cardinalnumber of from 1 to about 100 denoting an ethylene or poly(ethylene)moiety incorporated in the terpolymer chain; s is a cardinal number offrom 1 to about 100 denoting an epoxidized 5-ethylidene-2-norbornene oran epoxidized poly (5-ethylidene-2- norbornene) moiety incorporated inthe terpolymer chain; y is a cardinal number of from 1 to about 100denoting propylene or a poly(propylene) moiety incorporated in theterpolymer chain; z is a cardinal number from 0 to about 100 denotingS-ethylidene-Z-norbornene or a poly '(5-ethylidene-Z-norbornene) moietyincorporated in the terpolymer chain prior to epoxidation; and the sumof s and z may be in the range of 1 to about 100. It will be apparentthat the numerical values for s, x, y and 2. as used herein do notrepresent totals of any par ticular monomer unit in the terpolymer chainbut are average values for any particular monomer present as a moiety inthe polymer chain.

(3) Functional Adducts of'Expoxidized Terpolymers Functional adducts ofthe epoxidized terpolymers of this invention may be readily prepared byreaction of the epoxidized terpolymer with a functional reagent in thepresence of acidic or basic catalysts. Reaction of the oxirane with thenucleophilic reagent may proceed in two directions depending on thecatalyst. In the presence of acidic catalysts, the oxirane isprotonated, which may then readily react with a weak nucleophilicreagent; in the presence of basic catalysts, the unprotonated epoxide isreadily attacked by the stronger nucleophilic reagent. In either case adifunctional compound results as illustrated below:

HH IIH-l-II II Functional adduct Non-limiting examples of suitablefunctional reagents are: water, C to C alcohols, C to C preferably C toC monobasic acids, C to C amines, C to C amides, phenol, thiophenol,alkyl phenols or thiophenol with 1 to 4 alkyl groups of 1 to 12 carbonseach, C to C alkyl mercaptans, dialkylamino-phenols,N,N-dialkylaminoarylene diamines, alkyl imidazolines, aryl etheralcohols, alkyl ether alkylene amines and the like.

Further descriptions of preferred forms of some of these functionalagents follow:

The C to C alcohols can be branched or unbranched, saturated, aliphatic,aromatic, primary, secondary, or tertiary alcohols, preferablymonohydric alcohols, but including ether alcohols. Particularlypreferred are polyhydric alcohols of 2 to 6 hydroxy groups as well asamino alcohols. Examples include methanol, isopropanol, C Oxo alcohol,lauroyl alcohol, benzyl alcohol, ethylene glycol, monododecyl ether oftriethylene glycol, glycerol, pentaerythritol, glucose,dipentaerythritol, sorbitol, Cellosolve, Carbitol, diethanolamine, etc.

The C to C preferably C to C monobasic acids, can be branched orunbranched, saturated, aliphatic, monocarboxylic acids, preferably thesaturated fatty acids, such as acetic acid, butyric acid, caproic acid,lauric acid, etc.

The C to C amines can be branched or unbranched saturated, aliphatic,primary or secondary amines, containing 1 to 8 nitrogens, preferablymono or diamines, such as ethyl amine, butylamine, sec. butylamine,diethylamine, etc., but including higher polyamines such as alkylenepolyamines, wherein pairs of nitrogen atoms are joined by alkylenegroups of 2 to 4 carbon atoms. Thus, polyamines of the formula:

are included where n is 2 to 4 and m is 0 to 6. Examples of suchpolyamines include tetraethylene pentamine, tripropylene tetramine,N-aminoalkyl piperazines, e.g., N-(2- aminoethyl) piperazine,N,N'-di(2-aminoethyl) piperazine, etc. Particularly preferred are the Cto C N,N- dialkylamino alkylene diamines such as N,N-dimethyl-1,3-propane-diamine, etc. Also, preferred is tetraethylene pentamine, aswell as corresponding commercial mixtures such as Polyamine H, andPolyamine 500.

The C to C amides can be monoamides made from the above amines andmonobasic acids with the total number of carbon atoms in the amide inthe range of 2 to 18 carbons.

The alkyl phenols or thiophenols are those with 1 to 4 alkyl groups,preferably averaging 1 to 2 alkyl groups, wherein the alkyl groups eachcontain 1 to 12 carbon atoms which can be straight chain or branchedchain,

such as cresol, n-octyl phenol, di-n-octyl phenol, monoisobutylthiophenol, etc.

The C to C alkyl mercaptans can have branched or straight chain alkylgroups, and include ethyl mercaptan, n-octyl mercaptan, iso-octylmercaptan, lauryl mercaptan, etc.

Usually from 0.1 to 1 molar proportion of said functional reagent willbe reacted per molar proportion of epoxide present in the terpolymer. Inthe case of polyfunctional reagents, such as polyamines or polyols, thenpreferably 0.5 to 1.0, e.g., 0.8 to 1.0 molar proportion of saidpolyfunctional reagent is used in order to minimize cross-linkingbetween polymer chains and thus minimize formation of oil-insolubleportions. Of course, with a lower molecular weight terpolymer, and/orwith a low proportion of epoxide groups in the terpolymer, suchcross-linking may not be a problem thus permitting the use of arelatively low molar proportion of the polyfunctional reagent, e.g.,tetraethylene pentamine, relative to the molar proportion of epoxidegroups which are present. On the other hand, with a high molecularweight starting terpolymer, and/or a terpolymer with a high proportionof epoxide groups present, then a relatively large molar proportion oreven an excess molar proportion, e.g., 10% excess, of the polyfunctionalreagents will generally be desirable to prevent excessive cross-linkingand possible gelling and oil-insolubility. In any case, the desired endproduct is an oil-soluble product, e.g., at least 0.1 wt. percentsoluble in conventional mineral lubricating oil.

Various mixtures in any proportion of functional reagents outlinedabove, may be reacted with the epoxidized terpolymer, e.g., mixtures ofalcohol and amine, etc. In addition, any of the above functional agents,may also have other substituents, which substituents do not react withthe oxirane groups, and which do not interfere with the reaction of thefunctional group with the oxirane groups.

The reaction product of this invention can be incorporated inlubricating oil compositions, e.g., automotive crankcase oils, inconcentrations within the range of about 0.1 to about 10, e.g., 0.1 to3, weight percent based on the weight of the total compositions. Thelubricating oils to which the additives of the invention can be addedinclude not only mineral lubricating oils, but synthetic oils also.Synthetic hydrocarbon lubricating oils may also be employed, as well asnonhydrocarbon synthetic oils, includ ing dibasic acid esters such asdi-2-ethyl hexyl sebacate, carbonate esters, phosphate esters,halogenated hydrocarbons, polysilicones, polyglycols, glycol esters suchas C oxo acid diesters of tetraethylene glycol, etc. When used ingasoline or fuel oil, e.g., diesel fuel, No. 2 fuel oil, etc., thenusually about .001 to .5 wt. percent, based on the weight of the totalcomposition of the reaction product will be used. Concentratescomprising a minor proportion, e.g., 10 to 45 wt. percent, of saidreaction product in a major amount of hydrocarbon diluent, e.g., to 55wt. tives present, can also be prepared for ease of handling. percentmineral lubricating oil, with or without other addi- In the abovecompositions or concentrates, other conventional additives may also bepresent, including dyes, pour point depressants, antiwear agents. e.g.,tricresyl phosphate, zinc dialkyl dithiophosphates of 3 to 8 carbonatoms, antioxidants such as phenyl-alpha-naphthylamine, tert.octylphenol sulfide, bis-phenols such as 4,4'-methylene'bis(2,6-di-tert. butylphenol), viscosity index improvers such as theethylene-higher olefin copolymer, polyme-th acrylates, polyisobutylene,alkyl fumarate-vinyl acetate copolymers, and the like as well as otherashless dispersants or detergents.

While the above has described the invention in considerable detail, thefollowing examples more fully describe the invention and illustrate theadvance over the prior art.

EXAMPLE 1 Thirty grams of an ethylene-propylene-5-ethylidene-2-norbornene terpolymer containing 49 percent by weight of ethylene, 47.5percent by weight of propylene, 3.5 percent by weight ofS-ethylidene-2-norbornene and a viscosity average molecular weight (M of150,000 was dissolved in 800 ml. of chloroform contained in a 1 literflask fitted with a stirrer, droppingfunnel and thermometer. A solutionof 1.96 grams of metachloroperbenzoic acid (85% purity) in 40 ml. ofchloroform was added dropwise to the stirred polymer solution over thecourse of one-half hour. During the addition, the temperature of thereaction mixture rose from 25 C. to 28 C. indicating reaction. Thehomogeneous solution was allowed to stand overnight (16 hours) and wasthen poured in a slow stream into 4 liters of methanol with rapidstirring. The precipitated product was filtered on a Biichner funnel,washed with a further quantity of methanol and dried under vacuum. Thedried product weighed 29.2 grams (some mechanical loss) and exhibited astrong absorption band at 8.0 microns and two moderate adsorption bandsat 11.2 and 12 microns when examined by infrared spectroscopy, showingthe presence of oxirane functionality. Analysis showed an oxygen contentof 0.55 wt. percent.

EXAMPLE 2 The experimental procedure of Example 1 was repeated with 30grams of a terpolymer containing 45 percent by weight of ethylene, 46percent by weight of propylene, 9.0 percent by weight of-ethylidene-2-norbornene and a M of 165,000. 5.02 grams of themeta-chloroperbenzoic acid dissolved in 50 ml. of chloroform was addedto the terpolymer dissolved in 800 ml. of chloroform. The epoxidizedterpolymer was worked up and isolated in the same manner as the productin Example 1. The product Weighed 27.6 grams, exhibited absorption at8.0, 11.2 and 12 microns by infra-red analysis and had an oxygen contentof 1.15 percent by weight.

EXAMPLE 3 Three grams of the epoxidized product of Example 1 was mixedwith 0.50 gm. of N,N-dimethyl-1,3-propanediamine, 0.004 gm. of p-toluenesulfonic acid and 50 ml. of 1,2,4-trichlorobenzene in a 200 ml. flaskfitted with a reflux condenser and nitrogen purge line. The mixture washeated under nitrogen for 7 hours at a temperature of 170 175 C., cooledto room temperature and worked up in methanol. Purification was attainedby re-solution in toluene and reprecipitation in methanol. Analysis ofthe dried product, which weighed 2.68 grams showed a nitrogen content of0.16 weight percent.

EXAMPLE 4 The procedure of Example 3 was repeated with the product ofExample 2. Three grams of the epoxidized product of Example 2, 1.0 gm.of N,N-dimethyl-l,3-propanediamine, 0,004 grams of p-toluene sulfonicand 50 ml. of 1,2,4-trichlorobenzene were heated for 7 hours at 170- 175C. under an atmosphere of nitrogen. Reprecipitated dry product weighed2.69 grams and showed on analysis a nitrogen content of 0.20 weightpercent.

EXAMPLE 5 The epoxidized terpolymer products of Examples 1 and 2 and thefunctional adducts of Examples 3 and 4 were made up as wt. percentconcentrates in Solvent 150 Neutral Oil which is a solvent extracted,neutral, paraffinic oil having a viscosity of 150 SUS at 100 F. asdetermined by ASTM D567.

Aliquots of the concentrates were dissolved in a used automobilecrankcase mineral lubricating oil and tested for ability to maintainsludge in a dispersed state by means of a sludge inhibition bench test.

The concentrations used are shown in Table I. After dissolving theepoxidized polymers the samples were heated at 280 F.i2 F. for 1 6hours. After this length of time the amount of sludge that is notdispersed by the additive was measured by centrifuging the samples at2000 rpm.

for 30 minutes. The oil was carefully decanted from the sludge and thesludge was then washed twice with 25 cc. of n-pentane. After washing,the sludge was dried at room temperature to constant weight (about 1hour). Blanks were also run on used oil containing no additive todetermine total sludge. The percentage of sludge dispersed by theadditives were then calculated as set forth in Table I.

TABLE I Concentration,

gms. polymer/1O Percent sludge gms. used oil dispersed Polymer ofExample 1.

Example 2.

OQKRN cones:

Example 3 Example 4..-"

Thickening Efiiciency of Functional Adducts Thickening efficiency 1Product of Example 3 1.9 Product of Example 4 2.7

1 Thickening efficiency is defined as the ratio of the weight perc entof Enjay Chemical Co. Paratone N (a polyisobutylene of Mv 125,000 asdetermined in diisobutylene at 20 C. according to the relationship[n]:36 10- Mv-* required to thicken Solvent 150 Neutral Oil to aviscosity of 12.4 centistokes at 210 F. to the weight of theexperimental polymer required to thicken the same oil to the sameviscosity at the same temperature.

As seen by the above example, oil soluble expoxidized terpolymers, ortheir functional adducts, of the invention can be made as automotivecrankcase oil dispersants and can also be effective in neutralizingacidity in lubricants in which they are compounded.

The epoxidized terpolymers and their functional adducts are compatiblewith and form substantially hazefree solutions at effectiveconcentrations in the range of 0.1 to 10 weight percent in neutral oilswhich are herein defined as paraffinic or naphthenic distillatelubricating oils which have viscosities in the range of 50 to 1000 SUSat 100 F. or are synthetic lubricants, particularly of the ester type.The neutral oils may have been refined by any of the procedures wellknown to those having skill in the art and may be further compoundedwith antioxidants, oiliness agents and the like as hereinbeforeindicated.

What is claimed is:

1. A composition comprising a major amount of a hydrocarbon fuel orlubricating oil and .001 to 45 wt. percent of an oil soluble adduct ofan epoxidized terpolymer, useful as a lubricant or fuel additive, saidterpolymer having a molecular weight in the range of 10,000 to 1,000,000viscosity average molecular weight and comprising in the range of about30 to mole percent ethylene, about 14.5 to about 69.5 mole percent of aC to C alpha monoolefin and about 0.5 to about 20 mole percent of a C toC non-conjugated diolefin, wherein about 10 to of the double bonds inthe terpolymer have been epoxidized, and about 10 to 100% of theepoxidized groups have been reacted with a C to C amine which contains 1to 8 nitrogen atoms to form said adduct.

2. A composition according to claim 1, wherein said composition is alubricating composition comprising a major amount of mineral lubricatingoil containing 0.1 to 10.0 wt. percent of said functional adduct.

3. A composition according to claim 2, wherein said amine is apolyamine.

4. A composition according 'to claim 3, wherein said C to C alphamonoolefin is propylene.

5. A composition according to claim 4, wherein said terpolymer is aterpolymer of about 40 to 70 mole percent ethylene, about 20 to 58 molepercent propylene and about 2 to 10 mole percent ofS-ethylidene-2-norbornene.

6. A composition according to claim 5, wherein said amine isN,N-dimethyl-1,3-prpylene diamine.

References Cited UNITED STATES PATENTS Whitney 252-55 X Dorer 252-515 ATakashima et al 252-55 Takashima et a1 252- Jacobson et a1 44-62 XHonnen et al. 252- Abbott 252-515 A US. Cl. X.R.

P0405) UNITED STATES PATENT OFFICE CERIIIICATIL OF CORRECTION i PatentNo. 3,842,010 Dated October 15, 1974 v lnventofls) James J. Pa-ppas;florman Jacobson and Edward N. Kresge It is certified that error appearsin the above-identified patent and that said Letters Patent are herebycorxectei as shown below;

Page 1, ,column 1, line "4 cahcel "'Jacob'sen" and substitute--Jacobson--.

Signed an l sealed this 7th day of Januafy 1975.

- (SEAL) Attest: I McCOY M. GIBSON JR. c. MARSHALL DANN AttestingOffieer rCommi-ssioner of Patents a

1. A COMPOSITION COMPRISING A MAJOR AMOUNT OF A HYDROCARBON FUEL ORLUBRICATING OIL AND .001 TO 45 WT. PERCENT OF AN OIL SOLUBLE ADDUCT OFAN EPOXIDIZED TERPOLYMER, USEFUL AS A LUBRICANT OR FLUEL ADDITIVE, SAIDTERPOLYMER HAVING A MOLECULAR WEIGHT IN THE RANGE OF 10.000 TO 1,000,000VISCOSITY AVERAGE MOLECULAR WEIGHT AND COMPRISING IN THE RANGE OF ABOUT30 TO 85 MOLE PERCENT ETHYLENE, ABOUT 14.5 TO ABOUT 69.5 MOLE PERCENT OFA C3 TO C8 ALPHA MONOOLEFIN AND ABOUT 0.5 TO ABOUT 20 MOLE PERCENT OF AC5 TO C14 NON-CONJUGATED DIOLEFIN, WHEREIN ABOUT 10 TO 100% OF THEDOUBLE BONDS IN THE TERPOLYMER HAVE BEEN EPOXIDIZED, AND ABOUT 10 TO100% OF THE EPOXIDIZED GROUPS HAVE BEEN REACTED WITH A C1 TO C18 AMINEWHICH CONTAINS 1 TO 8 NITROGEN ATOMS TO FORM SAID ADDUCT.